EP0512031A1 - Composition detergente de blanchissage. - Google Patents

Composition detergente de blanchissage.

Info

Publication number
EP0512031A1
EP0512031A1 EP91903612A EP91903612A EP0512031A1 EP 0512031 A1 EP0512031 A1 EP 0512031A1 EP 91903612 A EP91903612 A EP 91903612A EP 91903612 A EP91903612 A EP 91903612A EP 0512031 A1 EP0512031 A1 EP 0512031A1
Authority
EP
European Patent Office
Prior art keywords
composition according
chain
attached
acyl
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP91903612A
Other languages
German (de)
English (en)
Other versions
EP0512031B1 (fr
Inventor
Ture Damhus
Ole Kirk
Frederick Edward Hardy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novo Nordisk AS
Procter and Gamble Co
Original Assignee
Novo Nordisk AS
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Novo Nordisk AS, Procter and Gamble Co filed Critical Novo Nordisk AS
Publication of EP0512031A1 publication Critical patent/EP0512031A1/fr
Application granted granted Critical
Publication of EP0512031B1 publication Critical patent/EP0512031B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
    • C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
    • C07H13/04—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals attached to acyclic carbon atoms
    • C07H13/06—Fatty acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
    • C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
    • C07H13/08—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals directly attached to carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/391—Oxygen-containing compounds
    • C11D3/3912—Oxygen-containing compounds derived from saccharides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds

Definitions

  • This invention relates to a bleaching detergent composition, to a washing and bleaching liquor, and to a washing and bleaching process. More specifically, these comprise a hydrogen peroxide source and a bleach activator. The invention also relates to a compound for use as a bleach activator.
  • detergents comprising peroxygen bleaches such as sodium perborate (PB) or sodium percarbonate (PC) are effective in removing stains from textiles.
  • PB sodium perborate
  • PC sodium percarbonate
  • the bleaching effect at temperatures below 50 ⁇ C can be increased by using a peracid precursor (bleach activator) such as tetraacetylethylenediamine (TAED) , nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934), 3,5,5-trimethylhexanoyloxybe ⁇ zenesulfonate (ISONOBS, described in EP 120,591), or pentaacetylglucose (PAG), which is perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect.
  • TAED tetraacetylethylenediamine
  • NOBS nonanoyloxybenzenesulfonate
  • ISONOBS 3,5,
  • EP 325,100 proposes use of an acetylated sugar ether containing a long-chain alkyl group as a bleach activator. However, such compounds cannot be easily prepared.
  • sugar derivatives have bleach- activating effect both on "hydrophilic” stains (e.g. tea or red wine) and on "hydrophobic” stains (e.g. grass or tomato sauce).
  • the compounds in question are derivatives of pentoses or hexoses, having a long-chain acyl group and one or more short-chain acyl or aroyl groups attached through ester bonds.
  • a short-chain alkyl group is attached through a glycosidic bond.
  • the invention provides a bleaching detergent composition
  • a bleaching detergent composition comprising a source of hydrogen peroxide and a compound of the general formula (A-CO-) (R'-CO-) n X -R" y (I) wherein
  • X is a pentose or hexose sugar moiety
  • A-CO is a long-chain acyl group, whereby A is one of the following: a C- 7 -C.
  • R is Cg-C- j hydrocarbyl, p is 0, 1 , 2 or 3, q is 1-5, r is 2-4, R'-CO is a C 2 -C short-chain acyl or aroyl group, R" is a C ⁇ -C 4 alkyl group, y is 0 or 1 , and n is 1, 2, 3 or 4, whereby the alkyl group R (if present) is attached through a glycosidic bond to the anomeric C atom, and the acyl groups are attached through ester bonds.
  • n+y cannot exceed 3 for a pentose and 4 for a hexose.
  • the invention also provides a washing and bleaching liquor comprising a hydrogen peroxide source and the above-described compound of formula (I), and a washing and bleaching process in the presence of these.
  • the invention provides novel compounds of formula (I).
  • Another aspect provides compounds of formula (I) wherein the long- chain acyl group excludes straight-chain saturated C 8 and C ⁇ 2 -C 20 acyl and wherein it is attached to the anomeric C atom.
  • These compounds are novel and are particularly effective in the bleaching of hydrophobic stains.
  • the invention uses a hydrogen peroxide source as a bleaching agent, i.e. a compound that provides hydrogen peroxide in an aqueous detergent solution.
  • a hydrogen peroxide source i.e. a compound that provides hydrogen peroxide in an aqueous detergent solution.
  • Examples are hydrogen peroxide itself, perborates such as sodium perborates and percarbonates such as sodium percarbonate.
  • Sugar derivatives such as sodium percarbonate.
  • the sugar derivatives according to the invention consist of a pentose or hexose sugar moiety, substituted with a long-chain acyl group and one or more short-chain acyl or aroyl groups through ester bonds, and optionally substituted with a short-chain alkyl group through a glycosidic bond.
  • the long-chain fatty acyl group may be saturated, mono- or poly- unsaturated; straight-chain or branched-chain, preferably C3-C13.
  • Some preferred acyl groups are octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tetra- decanoyl, hexadecanoyl, octadecanoyl, 10-undecenoyl, oleoyl, 2-ethyl-hexanoyl and
  • Cg-C-* 2 hydrocarbyl groups are particularly preferred as they provide good bleach activation on hydrophobic stains.
  • the short-chain acyl or aroyl group is preferably a C 2 -Cg acyl group (especially acetyl) or benzoyl. Such derivatives can be prepared conveniently and economically.
  • the sugar moiety may be an aldohexose or aldopentose.
  • glucose or xylose derivatives are preferred.
  • the sugar moiety may be a ketohexose or ketopentose.
  • fructose derivatives are preferred.
  • the glycoside bond may be in the ⁇ - or ⁇ -anomeric form.
  • compounds having one of the acyl- groups attached to the anomeric C-atom are preferred as they are most rapidly perhydrolyzed.
  • This acyl group may be in the a- or ⁇ -anomeric position.
  • Sugar esters having a long- chain acyl group (as specified above) attached to the anomeric C-atom are preferred, as they are particularly efficient for bleaching hydrophobic stains.
  • sugar esters having a short-chain acyl group (e.g. an acetyl group) attached to the anomeric C-atom may be preferred, as they are particularly efficient for bleaching hydrophilic stains.
  • the sugar derivatives may be in the pyranose or furanose form.
  • n+y + 1 of acyl and alkyl substituents in the sugar molecule may vary from 2 up to 4 for a pentose or up to 5 for a hexose.
  • Sugar derivatives with the long-chain acy group attached to a side chain of the sugar molecule i.e. to the 6-position of glucose or the 1- or 6- position of fructose
  • the bleaching detergent composition of the invention will generally be provided in particulate form.
  • the sugar derivative of formula (I) should be present in crystalline form, and for good crystallization it is preferable to use the sugar derivative in pure form rather than a mixture of isomers. For compounds substituted at the anomeric C atom this implies use of either the ⁇ - or the 0-form rather than a mixture of these.
  • Some preferred compounds are 2,3,4,6-tetra-0-acetyl-1-0-(long-chain acyl)-glucose in ⁇ - or 0-form where the long-chain acyl is one of the following: octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, 10-undecenoyl, 3,5,5- trimethylhexanoyl or 2-ethylhexanoyl.
  • the peroxide bleach and the sugar derivative (bleach activator) are preferably mixed in a molar ratio of 1 :10 to 20:1, preferably 1 :1 to 10:1.
  • the amount of peroxide bleach in the composition is preferably 1-
  • the amount of bleach activator is preferably 2-90%, e.g. 2-50%, especially 5-30% (percentages by weight).
  • composition of the invention may comprise other surfactants, e.g. of the non-ionic and/or anionic type.
  • nonionics are alcohol ethoxylates (AE), nonylphenol ethoxylates, alkyl polyglycosides (APG), and monoesters of carbohydrates (e.g. of free sugars or of glycosides).
  • anionics are linear alkylbenzene sulfonates (LAS), fatty alcohol sulfates, fatty alcohol ether sulfates (AES), ⁇ -olefin sulfonates (AOS) and soaps.
  • composition of the invention may contain other conventional detergent ingredients such as suds-controlling agents, foaming boosters, chelating agents, ion exchangers, alkalis, builders, cobuilders, other bleaching agents, bleach stabilizers, fabric softeners, anti-redeposition agents, enzymes, optical brighteners, anti-corrosion agents, fragrances, dye-stuffs, blueing agents, formulation aids, fillers and water.
  • detergent ingredients such as suds-controlling agents, foaming boosters, chelating agents, ion exchangers, alkalis, builders, cobuilders, other bleaching agents, bleach stabilizers, fabric softeners, anti-redeposition agents, enzymes, optical brighteners, anti-corrosion agents, fragrances, dye-stuffs, blueing agents, formulation aids, fillers and water.
  • composition of the invention may be provided in liquid form or in powder or granular form. It may be formulated in analogy with the frame formulations for powder detergents given at p. 288 of J. Falbe: Surfactants in Consumer Products. Theory, Technology and Application, Springer-Verlag 1987 by replacing all or part (e.g. 50%) of the non-ionic surfactant with ester according to the invention.
  • washing liquor of the invention can be obtained by dissolving the above-described detergent in water, or the ingredients can be added and dissolved separately.
  • the total detergent concentration will be 1-20 g/l
  • the amount of the hydrogen peroxide source will be 0.05-5 g/l, especially 0.25-1 g/l (calculated as sodium perborate monohydrate)
  • the amount of the sugar derivative will be 0.1-2.5 g/l, especially 0.25-1.5 g/l.
  • the washing process of the invention is typically carried out with the above-described liquor at temperatures of 20-60° C for 10-60 minutes in a conventional washing machine.
  • Figs. 1 - 3 and 5 show bleach activation at varying concentrations of three different sugar derivatives according to the invention on three different soilings.
  • Fig. 4 shows a similar comparison of three sugar derivatives according to the invention and two prior-art bleach activators. Details are given in Example 5.
  • the preparations of the sugar derivatives were generally mixtures of the ⁇ - and /3-anomers. In all cases satisfactory 1 H-NMR spectra were obtained for the preparations. The preparations were all approximately 90% pure, but were dosed in the bleaching experiments as if 100% pure.
  • inventive sugar derivatives were added to the various test-solutions as either methanol or ethanol solutions, while TAED, PAG, and ISONOBS were added directly. It has been checked that methanol/- ethanol at the levels attained by adding the sugar derivatives in this way have no influence in the experiments performed.
  • This example is concerned with an examination of glucose ester and glycoside ester preparations as activators for hydrogen peroxide in the bleaching of test swatches soiled with tea, red wine, or grass.
  • test swatches used were prepared by homogeneously soiling cotton cloth with tea, red wine, or grass juice, and then air-drying the soiled cloth overnight in the dark.
  • the resulting material was stored in the dark at 4 ⁇ C (tea, red wine) or below 0°C (grass) for at least 2 weeks before cutting test swatches.
  • the experiments were carried out as small-scale analogues of a Terg- o-tometer washing trial, i.e. isothermally in a series of beakers with concerted stirring (and alternating stirring direction).
  • the soiled textile was loaded to 9 g/l washing liquor.
  • the washing liquor employed was a 50 mM sodium carbonate buffer at pH 10.5 with 0.4 g nonionic surfactant/I added (the preparation Berol 160 from Berol Nobel was used, a C ⁇ 2 -C ⁇ 4 fatty alcohol ethoxylate with an EO value of 6).
  • the washing liquor was prepared from demineralized water. Washing temperature was 40" C. Duration: 30 min.
  • preparation 1 is 1-0-acetyl-6-0-octanoylglucose
  • preparations 2 and 3 are 2-O-acetyl and 3-O-acetyl derivatives of ethyl 6- O-decanoylglucopyranoside, respectively.
  • the activator TAED (tetraacetylethylenediamine) was used for a comparison and was dosed to 1 mM, since it possesses 2 perhydrolyzable acetyl groups. Standard deviations were in all cases below 1 remission unit.
  • the three sugar derivative preparations thus all show benefits compared to using H 2 0 2 alone; all are superior to TAED in removing grass stains; and preparation 1 is superior to TAED on tea and red wine as well.
  • This example is concerned with an examination of some further sugar derivative preparations as activators for hydrogen peroxide.
  • the experimental setup was as described in Example 1.
  • preparation 4 is 1-0-acetyl-6-0-decanoylgiucose
  • preparation 5 is 2,3,4-tri-0-acetyl-6-0-octanoyl-glucose
  • preparations 6 and 7 are 2,3-di-O-acetyl and 2,3,4-tri-O-acetyl derivatives of ethyl 6-O-decanoylgluco- pyranoside, respectively.
  • the sugar derivative preparations were dosed to 2 mM except preparations 6 and 7 which were dosed in the same weight amount as prepara ⁇ tions 2 and 3 in Table 1. The results are shown in Table 2.
  • 6-O-acylglucose with acyl octanoyl, decanoyl, dodecanoyl, tetradecanoyl, and hexadecanoyl were tested.
  • the experimental conditions were: 10 mM H 2 0 2 in 50 mM sodium carbonate buffer (prepared from demineralized water) at pH 10.5 with 0.4 g nonionic surfactant/I added (the preparation Berol 160 from Berol Nobel was used, a C-J2-C-I4 fatty alcohol ethoxylate with an EO value of 6). TAG-6-8 was dosed to a level of 2 mM.
  • Table 3 The results are shown in Table 3:
  • TAG-6-8 should be a very efficient activator for peroxide compounds since 3 mM peracid is formed in only 3 minutes from a 2 mM solution of TAG-6-8.
  • TAG-6-8 1 ,2,3,4-tetra-0-acetyl-6-0- octanoylglucose and TAG-6-10, the corresponding decanoyl derivative, were subjected to a study of effect versus increasing dosage, again under the small- scale washing conditions described in Example 1.
  • the hydrogen peroxide concentration was kept constant at 10mM while varying the activator concentration.
  • Figures 1 and 2 graph the results.
  • TAG-6-8 also presented in Example 4 for its peracid formation, bleaches the hydrophobic as well as the hydrophilic stains.
  • the C 8 and C-J Q compounds behave more or less identically on red-wine and tea stains, while the C10 compound is clearly superior on grass.
  • dose-effect studies analogous to the above ones are presented in Figures 3 and 5.
  • This example compares the bleaching efficacy of a wash liquor containing 2,3,4,6 tetra-0-acetyl-1-0-decanoylglucose (TAG-1-10), a derivative in accordance with the present invention, with that of a wash liquor containing each of several prior art bleach activators, viz. sodium 3,5,5-trimethylhexanoyloxyben- zenesulfonate (ISONOBS), pentaacetylglucose (PAG) and tetraacetylethylene- diamine (TAED).
  • ISONOBS sodium 3,5,5-trimethylhexanoyloxyben- zenesulfonate
  • PAG pentaacetylglucose
  • TAED tetraacetylethylene- diamine
  • the wash liquor contained 1% by weight of a detergent composition comprising (in weight percent).
  • the wash liquor was prepared as a stock solution of all of the components except the perborate bleach and activator which were added as weighed amounts into the pot immediately before the test commenced.
  • the TAG- 1-10 (as a preparation with an a: ⁇ anomer ratio of approx. 3:1) was added directly into the pot containing the wash liquor and dispersed using a high speed mixer.
  • Each pot was loaded with a series of circular cotton fabric swatches soiled with tea, wine, paprika and tomato stains.
  • the tea and wine stains were used to evaluate hydrophilic stain bleaching and were judged instrumentally by a Hunter Colour Reflectance Meter.
  • the paprika and tomato stains were used to assess hydrophobic stain removal and were assessed visually by an expert panel using a paired comparison technique.
  • the panellists' preferences are expressed in Panel Score Units (P.S.U.) on 1-5 Scheffe scale.
  • TAG-1-10 provides equivalent overall bleaching to PAG and TAED and, whilst not significantly better than ISONOBS on tea stains, it is significantly better on wine stains.
  • TAED and PAG give significantly poorer stain removal than ISONOBS whilst TAG-1-10 is at least as good as ISONOBS.
  • This example compares the stain removal performance of TAG-1-10 (see preceeding example), pentaacetylglucose (PAG) and tetraacetylethylene- diamine (TAED) in a split bundle washing trial in domestic washing machines.
  • the test employed Miele (Model W756) Washing Machines employing
  • hydrophobic stains painted on and aged similarly, were ragu sauce, tomato paste and siciliana sauce.
  • a number of naturally soiled articles were split ito two halves.one of which was washed using the TAED- containing product while the other was washed in a product containing either PAG or TAG-1-10.
  • the detergent product had the following composition in weight percent.
  • composition incorporating TAG-1-10 bleach activator demonstrates stain removal benefits across a wide variety of soils.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Certains dérivés de sucre ont une action blanchissante à la fois sur les taches "hydrophiles" (tels que le thé ou le vin rouge) et sur les taches "hydrophobes" (par exemple la graisse ou la sauce tomate). Les composés décrits sont des dérivés de pentoses ou d'hexoses, comportant un groupe acyle à chaîne longue et un ou plusieurs groupes acyles ou aroyle à chaîne courte fixés par l'intermédiaire de liaisons ester. Un groupe alkyle à chaîne courte peut éventuellement être fixé par l'intermédiaire d'une liaison glucosidique. Ces composés sont non toxiques et biodégradables et ils peuvent être avanteugeusement préparés par des procédés connus de la technique actuelle.
EP91903612A 1990-01-22 1991-01-22 Composition detergente de blanchissage Expired - Lifetime EP0512031B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DK017290A DK17290D0 (fr) 1990-01-22 1990-01-22
DK172/90 1990-01-22
CN90104771.6A CN1027079C (zh) 1990-01-22 1990-07-16 漂白洗涤剂组合物

Publications (2)

Publication Number Publication Date
EP0512031A1 true EP0512031A1 (fr) 1992-11-11
EP0512031B1 EP0512031B1 (fr) 1993-11-24

Family

ID=36763842

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91903612A Expired - Lifetime EP0512031B1 (fr) 1990-01-22 1991-01-22 Composition detergente de blanchissage

Country Status (18)

Country Link
EP (1) EP0512031B1 (fr)
JP (1) JPH05504159A (fr)
CN (3) CN1027079C (fr)
AR (1) AR246305A1 (fr)
AT (1) ATE97692T1 (fr)
AU (1) AU659081B2 (fr)
BR (1) BR9105955A (fr)
CA (1) CA2074178A1 (fr)
CS (1) CS13791A2 (fr)
DE (1) DE69100685T2 (fr)
DK (2) DK17290D0 (fr)
EG (1) EG19321A (fr)
ES (1) ES2060364T3 (fr)
IE (1) IE910193A1 (fr)
MA (1) MA22047A1 (fr)
NZ (1) NZ236856A (fr)
PT (1) PT96542A (fr)
WO (1) WO1991010719A1 (fr)

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DE19641708A1 (de) * 1996-10-10 1998-04-16 Clariant Gmbh Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats
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WO2005100530A1 (fr) * 2004-04-16 2005-10-27 Lg Household & Health Care Ltd. Activateur de blanchiment comprenant un compose alkyloxy, son procede de fabrication et composition de blanchiment le renfermant
JP5328183B2 (ja) * 2008-03-17 2013-10-30 国立大学法人 長崎大学 グルコシドエステル誘導体の製造方法
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CN107698629B (zh) * 2017-10-19 2021-01-19 上海科技大学 二硫键桥连去垢剂及其在膜蛋白研究中的应用
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WO2020160425A1 (fr) 2019-01-31 2020-08-06 Ecolab Usa Inc. Régulation des niveaux d'eau et de la concentration de détergent dans un cycle de lavage
WO2020160390A1 (fr) 2019-01-31 2020-08-06 Ecolab Usa Inc. Kit de machine à laver le linge permettant la commande des niveaux d'eau, la recirculation et la pulvérisation de produits chimiques
WO2020160429A1 (fr) 2019-01-31 2020-08-06 Ecolab Usa Inc. Dispositif de commande dun système de réutilisation d'eau de rinçage et procédés d'utilisation
US20200248383A1 (en) 2019-01-31 2020-08-06 Ecolab Usa Inc. Rinse water reuse system and methods of use
CN115052961A (zh) 2020-01-31 2022-09-13 埃科莱布美国股份有限公司 在器皿清洗应用中淀粉酶与氧漂白剂的协同作用
CA3196797A1 (fr) 2020-12-23 2022-06-30 Peter J. MCGRANE Adoucissant acide pour linge ayant une stabilite supplementaire et des avantages supplementaires d'attenuation d'incendie de linge et d'elimination de produit de protection solaire
WO2022140505A1 (fr) 2020-12-23 2022-06-30 Ecolab Usa Inc. Élimination de salissure sur du coton par un traitement lors de l'étape de rinçage pour un nettoyage amélioré lors d'un lavage ultérieur
CA3235421A1 (fr) 2021-12-22 2023-06-29 Ashish Dhawan Compositions comprenant de multiples composes cationiques charges anti-salissures

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JPH05504159A (ja) 1993-07-01
ATE97692T1 (de) 1993-12-15
CA2074178A1 (fr) 1991-07-23
CN1102209A (zh) 1995-05-03
IE910193A1 (en) 1991-07-31
ES2060364T3 (es) 1994-11-16
NZ236856A (fr) 1994-07-26
DE69100685T2 (de) 1994-03-17
EG19321A (en) 1995-06-29
WO1991010719A1 (fr) 1991-07-25
DK0512031T3 (da) 1994-04-18
EP0512031B1 (fr) 1993-11-24
PT96542A (pt) 1991-11-29
CN1027079C (zh) 1994-12-21
AU659081B2 (en) 1995-05-11
BR9105955A (pt) 1992-11-10
AR246305A1 (es) 1994-07-29
CN1058229A (zh) 1992-01-29
CN1030467C (zh) 1995-12-06
MA22047A1 (fr) 1991-10-01
AU7214191A (en) 1991-08-05
CS13791A2 (en) 1991-08-13
DE69100685D1 (de) 1994-01-05
CN1055951A (zh) 1991-11-06
DK17290D0 (fr) 1990-01-22

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